JP7076701B2 - A block copolymer and a method for producing the same, and a method for producing a structure including a phase-separated structure. - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Law ・ Proceedings of the Society of Polymer Science, Vol. 66, No. 2 [2017], Publication No. 2ESA05 Publication date: September 6, 2017 Public Interest Incorporated Association, Society of Polymer Science, 66th Polymer Discussion Meeting Sponsored by the Society of Polymer Science, Japan Venue: National University Corporation Ehime University Date: September 21, 2017

The present invention relates to a block copolymer and a method for producing the same, and a method for producing a structure including a phase-separated structure.

In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), there is a demand for a technique for processing a more delicate structure. In response to such demands, attempts have begun to form finer patterns by utilizing the phase-separated structure formed by self-assembly of block copolymers in which blocks that are incompatible with each other are bonded to each other. There is. (See, for example, Patent Document 1.).
In order to utilize the phase-separated structure of block copolymers, it is essential that the self-assembled nanostructures formed by microphase separation are formed only in a specific region and arranged in a desired direction. .. In order to realize these position control and orientation control, processes such as grapho epitaxy that controls the phase separation pattern by the guide pattern and chemical epitaxy that controls the phase separation pattern by the difference in the chemical state of the substrate have been proposed. (See, for example, Non-Patent Document 1).

Block copolymers form a regular periodic structure by phase separation. It is known that this periodic structure changes into a cylinder (columnar), a lamella (plate), and a sphere (spherical) depending on the volume ratio of the polymer component and the like, and the period depends on the molecular weight.
Attempts have been made to form a vertical cylinder shape in which the cylinder shape is vertically oriented, a horizontal cylinder shape in which the cylinder shape is horizontally oriented, and a vertical lamella shape in which the lamella shape is vertically oriented as a fine pattern. For example, Patent Document 2 attempts to improve the vertical orientation of a pattern by introducing a polar group into the side chain terminal of a block copolymer composed of polystyrene and a siloxane derivative.

Japanese Unexamined Patent Publication No. 2008-36491 Japanese Unexamined Patent Publication No. 2016-166323

Proceedings of SPIE, Vol. 7637, No. 76370G-1 (2010). Annu. Rev. Phys. Chem. 41 525 (1990)

In the method described in Patent Document 2, although the vertical orientation of the pattern is improved, there is room for improvement in the roughness improvement after etching.
Non-Patent Document 2 describes that the interface thickness (t) between block A and block B in a block copolymer composed of block A and block B satisfies the relationship of the following formula (1). There is.

［式中、ｔは、ブロックＡとブロックＢから構成されるブロック共重合体中のブロックＡとブロックＢとの界面厚を表す。ａは、モノマーの大きさを示すパラメータである。χは、相互作用パラメータであり、この値が大きいほど、相分離性能が高いことを意味する。］

[In the formula, t represents the interface thickness between block A and block B in the block copolymer composed of block A and block B. a is a parameter indicating the size of the monomer. χ is an interaction parameter, and the larger this value is, the higher the phase separation performance is. ]

As shown in the above equation (1), the larger the interaction parameter χ, the smaller the interface thickness t.
For example, in patterning using a block copolymer composed of block A and block B, the interface between block A and block B is the edge portion of the pattern in order to selectively remove one block by dry etching or the like. Will be equivalent to.
At the interface between the block A and the block B, a component constituting the block A and a component constituting the block B are mixed. Since the variation of the components at the interface can be a factor of the roughness after etching, it is expected that the roughness is improved by reducing the interface thickness t.
Generally, in a diblock copolymer having a large interaction parameter χ, the interface thickness t becomes small, but the surface free energy difference between blocks also becomes large. For this reason, there is a problem that blocks having a small surface free energy segregate on the surface of the block copolymer film during the thermal annealing treatment for forming the phase-separated structure, and as a result, it is difficult to form a vertical alignment pattern suitable for fine processing. rice field.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a block copolymer suitable for self-assembled lithography and a method for producing the same, and a method for producing a structure including a phase-separated structure. And.

The first aspect of the present invention is a first block composed of a polymer having a repeating structure of a structural unit (u1) containing no silicon atom, and a polymer having a repeating structure of a structural unit (u2) containing a silicon atom. A block copolymer comprising a second block of
The second block is
A block (b21) made of a polymer having a repeating structure of a structural unit (u21) represented by the following general formula (u2-1), and a block (b21).
A block (b22) made of a polymer having a repeating structure of a structural unit (u22) containing a silicon atom other than the structural unit (u21), and a block (b22).
Including
The block (b22) is a block copolymer located between the first block and the block (b21).

［式中、Ｒ^Ｐ２１１は、極性基を有する有機基、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ２１２は、極性基を有する有機基である。］

[In the formula, ^RP211 is an organic group having a polar group, an alkyl group, an alkyl halide group or a hydrogen atom. ^RP212 is an organic group having a polar group. ]

In the second aspect of the present invention, a polymer having a repeating structure of the structural unit (u11) represented by the following general formula (u1-1) or a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent. The step (a) of preparing a first block composed of a polymer having a repeating structure of a structural unit (u12) derived from an acrylic acid ester which may be used.
A siloxane or a monomer (m222) represented by the following general formula (m2-2-2) is addition-polymerized to the first block prepared in the step (a), and the first block and the block (b22) are subjected to addition polymerization. Step (b) of preparing a block copolymerization precursor bonded with and
The block copolymer precursor prepared in the step (b) is subjected to addition polymerization of a monomer (m21) for inducing a structural unit (u21) represented by the following general formula (u2-1), and the first step is carried out. The step (c) of preparing a block copolymer in which the block (b22) is located between the blocks (b21) and the block (c).
Have,
In the step (c), the reaction temperature when the monomer (m21) is addition-polymerized to the block copolymer precursor is set to the siloxane or the monomer (m222) in the first block in the step (b). ) Is a method for producing a block copolymer, which is set to a temperature lower than the reaction temperature at the time of addition polymerization.

［式中、Ｒ^Ｐ１１１は、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ１１２は、置換基を有していてもよい芳香族環式基である。
Ｒは、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｒ^Ｐ２２１は、２価の連結基である。Ｒ^Ｐ２２２は、ケイ素原子を有する有機基である。
Ｒ^Ｐ２１１は、極性基を有する有機基、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ２１２は、極性基を有する有機基である。］

[In the formula, ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom. ^RP112 is an aromatic cyclic group which may have a substituent.
R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. ^RP221 is a divalent linking group. ^RP222 is an organic group having a silicon atom.
^RP211 is an organic group having a polar group, an alkyl group, an alkyl halide group or a hydrogen atom. ^RP212 is an organic group having a polar group. ]

A third aspect of the present invention is the step (i) of forming a layer containing the block copolymer of the first aspect on the substrate.
In the step (ii) of phase-separating the layer containing the block copolymer,
Is a method for producing a structure including a phase-separated structure.

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of the hydrogen atom of the alkyl group or the alkylene group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
The “constituent unit derived from the acrylic acid ester” means a structural unit formed by cleaving the ethylenic double bond of the acrylic acid ester.
The "acrylic acid ester" is a compound in which the hydrogen atom at the terminal of the carboxy group of acrylic acid (CH ₂ = CH-COOH) is replaced with an organic group.
In the acrylic acid ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent that replaces the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom, for example, an alkyl group having 1 to 5 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and a hydroxy group. Examples thereof include an alkyl group. The carbon atom at the α-position of the acrylic acid ester is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylic acid ester. Further, the acrylic acid ester and the α-substituted acrylic acid ester may be collectively referred to as “(α-substituted) acrylic acid ester”.
The “constituent unit derived from the hydroxystyrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the hydroxystyrene derivative.
The term "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent, the hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group, or the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include a good hydroxystyrene benzene ring to which a substituent other than a hydroxyl group is bonded. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.
The "constituent unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative" means a structural unit formed by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The term "vinyl benzoic acid derivative" is a concept including a hydrogen atom at the α-position of vinyl benzoic acid substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent, the hydrogen atom of the carboxy group of vinyl benzoic acid is substituted with an organic group, and the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include a benzene ring of vinyl benzoic acid to which a substituent other than a hydroxyl group and a carboxy group is bonded. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
The "styrene derivative" means that the hydrogen atom at the α-position of styrene is substituted with another substituent such as an alkyl group or an alkyl halide group.
“Constituent unit derived from styrene” and “constituent unit derived from a styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like. tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like can be mentioned.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Further, as the hydroxyalkyl group as the substituent at the α-position, specifically, a group in which a part or all of the hydrogen atom of the above-mentioned “alkyl group as the substituent at the α-position” is substituted with a hydroxyl group can be mentioned. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, most preferably 1.
"Exposure" is a concept that includes general irradiation of radiation.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a block copolymer suitable for self-assembled lithography, a method for producing the block copolymer thereof, and a method for producing a structure including a phase-separated structure.

It is a schematic process diagram explaining one Embodiment example of the manufacturing method of the structure including the phase separation structure which concerns on this invention. It is a figure explaining one Embodiment example of an arbitrary process.

≪Block copolymer≫
The block copolymer according to the present embodiment has a first block made of a polymer having a repeating structure of a structural unit (u1) not containing a silicon atom, and a repeating structure of a structural unit (u2) containing a silicon atom. It includes a second block made of a polymer.
In the present embodiment, the "block copolymer" is a polymer to which a plurality of types of blocks (partial constituents in which the same type of constituent units are repeatedly bonded) are bonded. The number of types of blocks constituting the block copolymer may be two or more.

<1st block>
In the present embodiment, the first block is not limited as long as it is made of a polymer having a repeating structure of a structural unit (u1) containing no silicon atom, and is represented by, for example, the following general formula (u1-1). A polymer having a repeating structure of the structural unit (u11), or a repeating structure of the structural unit (u12) derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. Examples thereof include a block made of a polymer having the same.

［式中、Ｒ^Ｐ１１１は、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ１１２は、置換基を有していてもよい芳香族環式基である。］

[In the formula, ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom. ^RP112 is an aromatic cyclic group which may have a substituent. ]

(Constituent unit (u11))
In the general formula (u1-1), ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom.
The alkyl group of ^RP111 is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl). Group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Examples of the halogenated alkyl group of ^RP111 include a group in which a part or all of the hydrogen atom of the alkyl group is replaced with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among them, as ^RP111 , an alkyl group, an alkyl halide group or a hydrogen atom is preferable, an alkyl group having 1 to 5 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is preferable. Most preferred.

In the general formula (u1-1), ^RP112 is an aromatic cyclic group which may have a substituent.
Examples of the aromatic cyclic group of ^RP112 include a phenyl group, a naphthyl group, a biphenyl group, an anthrasenyl group, a pyridyl group and the like. Among them, as the aromatic cyclic group of ^RP112 , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent that the aromatic cyclic group of ^RP112 may have include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and an alkyl halide group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the alkyl halide group include a group in which a part or all of the hydrogen atom of the alkyl group is replaced with a halogen atom.

(Constituent unit (u12))
In the present embodiment, the constituent unit (u12) is derived from a constituent unit derived from methyl acrylate, a constituent unit derived from ethyl acrylate, a constituent unit derived from propyl acrylate, and n-butyl acrylate. Constituent unit derived from t-butyl acrylate, structural unit derived from cyclohexyl acrylate, structural unit derived from octyl acrylate, structural unit derived from nonyl acrylate, hydroxy acid acrylate. Constituent units derived from ethyl, constitutive units derived from hydroxypropyl acrylate, constitutive units derived from benzyl acrylate, constitutive units derived from anthracene acrylate, constituent units derived from glycidyl acrylate, acrylic. Constituent Units Derived from 3,4-Epoxycyclohexylmethane, Constituent Units Derived from Methyl Methacrylate, Constituent Units Derived from Ethyl Methacrylate, Constituent Units Derived from propyl Methacrylate, n-Butyl Methacrylate Constituent units derived from, t-butyl methacrylate, constitutive units derived from cyclohexyl methacrylate, constitutive units derived from octyl methacrylate, constituent units derived from nonyl methacrylate, methacrylic acid. Constituent units derived from hydroxyethyl acetate, structural units derived from hydroxypropyl methacrylate, structural units derived from benzyl methacrylate, structural units derived from anthracene methacrylate, and structural units derived from glycidyl methacrylate. , Constituent units derived from methacrylic acid 3,4-epoxycyclohexylmethane and the like.
Among these, the constituent unit (u12) is a constituent unit derived from methyl acrylate, a constituent unit derived from ethyl acrylate, a constituent unit derived from t-butyl acrylate, and a constituent unit derived from methyl methacrylate. Constituent units derived from, a structural unit derived from ethyl methacrylate, and a structural unit derived from t-butyl methacrylate are preferable.

<2nd block>
In the present embodiment, the second block is a block (b21) made of a polymer having a repeating structure of a structural unit (u21) represented by the following general formula (u2-1), and a block (b21) other than the structural unit (u21). It comprises a block (b22) made of a polymer having a repeating structure of a structural unit (u22) containing a silicon atom, and the block (b22) is located between the first block and the block (b21). ing.

［式中、Ｒ^Ｐ２１１は、極性基を有する有機基、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ２１２は、極性基を有する有機基である。］

[In the formula, ^RP211 is an organic group having a polar group, an alkyl group, an alkyl halide group or a hydrogen atom. ^RP212 is an organic group having a polar group. ]

(Constituent unit (u21))
In the general formula (u2-1), ^RP211 is an organic group having a polar group, an alkyl group, an alkyl halide group or a hydrogen atom.
Examples of the organic group in the "organic group having a polar group" of ^RP211 include a monovalent hydrocarbon group which may have a substituent. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

· · Aliphatic hydrocarbon group in R ^P211 The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group Examples of the linear or branched aliphatic hydrocarbon group include an alkyl group, an alkenyl group and an alkynyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and 2-. Examples thereof include alkyl groups having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) such as ethylhexyl groups, nonyl groups and decyl groups. Examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) such as a vinyl group, an allyl group, and a butenyl group. Examples of the alkynyl group include alkynyl groups having 2 to 20 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) such as an ethynyl group and a propynyl group.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, for example, an alicyclic hydrocarbon group or an alicyclic hydrocarbon group is linear or linear. Examples thereof include a group bonded to the terminal of a branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
Examples of the alicyclic hydrocarbon group include a 3- to 8-membered cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a cyclopentenyl group and a cyclohexenyl group. Examples thereof include a 3- to 8-membered ring cycloalkenyl group; a bridging ring-type hydrocarbon group having 4 to 20 carbon atoms (preferably 7 to 12 carbon atoms) such as an adamantyl group and a norbornyl group.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferable, and methoxy is preferable. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

Aromatic hydrocarbon group in R ^P211 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); an aromatic compound containing two or more aromatic rings. A group from which one hydrogen atom has been removed (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Examples thereof include groups in which one is substituted with an alkyl group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group) and the like. .. The carbon number of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

The polar groups in the "organic group having a polar group" of R ^P211 include -OH, -C (= O) OH, -O-, -C (= O)-, -C (= O) -O-, -SH, -SO ₃ H, -S-, -C (= S)-, -S (= O)-, -S (= O) _2- , -S (= O) ₂ -O-, -NH ₂ , -N =, -NH-, -C (= O) NH-, and the like can be mentioned.

In the general formula (u2-1), examples of the alkyl group of ^RP211 include the same as the alkyl group as the aliphatic hydrocarbon group in ^RP211 .
Examples of the halogenated alkyl group of R ^P211 include a group in which a part or all of the hydrogen atom of the alkyl group is replaced with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The structural unit (u21) is preferably a structural unit represented by the following general formula (u2-1-1).

［式中、Ｒは、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｒ^Ｐ２１３は、２価の連結基である。Ｒ^Ｐ２１４は、極性基を有する有機基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. ^RP213 is a divalent linking group. ^RP214 is an organic group having a polar group. ]

In the general formula (u2-1-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms or the alkyl halide group having 1 to 5 carbon atoms of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and a pentyl. Examples include a group, an isopentyl group, a neopentyl group and the like.
Examples of the halogenated alkyl group of R include a group in which a part or all of the hydrogen atom of the alkyl group is replaced with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among them, R is preferably a methyl group or a hydrogen atom.

In the general formula (u2-1-1), ^RP213 is a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like.

A divalent hydrocarbon group that may have a substituent:
When ^RP213 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

· · Aliphatic hydrocarbon group in ^RP213 The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. 1 to 4 are more preferable, and 1 to 3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ). _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups;- CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as CH ₂ CH ₂ CH _2- , −CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from the aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, the cyclic fat. Examples thereof include a group in which a group hydrocarbon group intervenes in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are preferable, and methoxy is preferable. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

Aromatic hydrocarbon group in ^RP213 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group from which two hydrogen atoms have been removed from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group from which one atom is further removed) and the like can be mentioned. The carbon number of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
Examples of the alkoxy group, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-A divalent linking group containing a heteroatom:
When ^RP213 is a divalent linking group containing a heteroatom, the preferred linking groups are -O-, -C (= O) -O-, -C (= O)-, and -OC. (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group or an acyl group. ), -S-, -S (= O) _2- , -S (= O) ₂ -O-, general formula-Y ²¹ -O-Y ^22- , -Y ²¹ -O-, -Y ^21- C (= O) -O-, -C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , -Y ²¹ -OC ( = O) -Y ^22- or -Y ²¹ -S (= O) ₂ -O-Y ^22- [In the formula, Y ²¹ and Y ²² each have an independent substituent. It is also a good divalent hydrocarbon group, where O is an oxygen atom and m "is an integer of 0-3. ] And so on.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). In the case of −, the H may be substituted with a substituent such as an alkyl group or an acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
General formula-Y ²¹ -O-Y 22-, -Y ^{21-O-, -Y 21 -} C (= O) -O-, -C ⁽ = O) -O-Y ²¹ -,-[Y ^21- C (= O) -O] _{m "} -Y 22-, -Y ²¹ - ^OC (= O) -Y ^{22- or -Y 21 -} S (= O) ₂ -O-Y ²² -Medium, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group is mentioned in the description as the divalent linking group. (A divalent hydrocarbon group which may have a substituent) is mentioned.
As ^Y21 , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0. Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- is represented by the formula-Y ²¹ -C ⁽ = O) -OY 22-. A group is particularly preferable. Among them, a group represented by the formula- (CH ₂ ) _a' -C (= O) -O- (CH ₂ ) b'-is preferable. In the formula, _a'is 1 to 1 to. It is an integer of 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b'is an integer of 1 to 10 and 1 to 8. Is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.

The ^RP213 is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably a linear or branched alkylene group having 1 to 6 carbon atoms. It is more preferably a linear or branched alkylene group having 1 to 3 carbon atoms.

In the general formula (u2-1-1), ^RP214 is an organic group having a polar group, and the same as the organic group having a polar group of ^RP211 in the general formula (u2-1) can be mentioned. Will be.
Examples of the organic group having a polar group of R ^P214 include a group represented by the following general formula ( ^RP214 -1), a group represented by the following general formula ( ^RP214-2 ), or a group represented by the following general formula ( ^RP214 -3). ) Is preferred.

［式中、Ｒ_Ｏは－ＯＨ、－Ｃ（＝Ｏ）ＯＨ、又は構造中に－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－若しくは－ＯＨを含む炭化水素基を表す。Ｒ_Ｓは－ＳＨ、－ＳＯ_３Ｈ、又は構造中に－Ｓ－、－Ｃ（＝Ｓ）－、－Ｓ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－若しくは－Ｓ（＝Ｏ）_２－Ｏ－を含む炭化水素基を表す。Ｒ_Ｎは－ＮＨ_２、又は構造中に－Ｎ＝、－ＮＨ－若しくは－Ｃ（＝Ｏ）ＮＨ－を含む炭化水素基を表す。］

[In the formula, RO is a hydrocarbon containing -OH, -C (= _O ) OH, or -O-, -C (= O)-, -C (= O) -O- or -OH in the structure. Represents a group. _RS is -SH, -SO _3H , or -S-, -C (= S)-, -S (= O)-, -S (= O) ₂ -or-S (= O) in the structure. Represents a hydrocarbon group containing ₂ -O-. RN represents a hydrocarbon group containing -NH ₂ or _-N =, -NH- or -C (= O) NH- in its structure. ]

In the general formula ( ^RP214 -1), RO is -OH, -C (= _O ) OH, or -O-, -C (= O)-, -C (= O) -O- in the structure. Alternatively, it represents a hydrocarbon group containing -OH.
The hydrocarbon group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is an aliphatic hydrocarbon group. It may be present or it may be an aromatic hydrocarbon group.
The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
As the aliphatic hydrocarbon group, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent may be used. Examples include alkenyl groups.

The cyclic group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is a cyclic hydrocarbon group. It is preferable that the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The aromatic hydrocarbon group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is the above-mentioned formula (u1-). Examples thereof include the aromatic hydrocarbon ring mentioned in the divalent aromatic hydrocarbon group in ^RP13 in 1-1), or an aryl group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings. , A phenyl group and a naphthyl group are preferable.
The cyclic aliphatic hydrocarbon group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is the above-mentioned formula ( Examples thereof include the monocycloalkane mentioned in the divalent aliphatic hydrocarbon group in ^RP13 in u1-1-1) or the group obtained by removing one hydrogen atom from the polycycloalkane, and a cyclopentyl group and a cyclohexyl group are preferable.

As a substituent in the cyclic hydrocarbon group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO, for example. , Alkyl group, alkoxy group, halogen atom, alkyl halide group, hydroxyl group, carbonyl group, nitro group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable, and methoxy. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
As the alkyl halide group as a substituent, a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are described above. Examples include groups substituted with halogen atoms.

The chain-like alkyl group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is linear or linear. It may be in the form of a branched chain.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. Examples thereof include a group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group and the like.
The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

The chain alkenyl group in the "hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO is linear or linear. Any of the branched chains may be used, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylpropenyl group and a 2-methylpropenyl group.

As a substituent in a chain alkyl group or alkenyl group in "a hydrocarbon group containing -O-, -C (= O)-, -C (= _O ) -O- or -OH in the structure" of RO Is, for example, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and "-O-, -C (= _O )-, -C (= in the structure of the above RO". O) A cyclic group in "a hydrocarbon group containing -O- or -OH" and the like can be mentioned.

As the group represented by the general formula ( ^RP214 -1), the groups represented by the following chemical formulas ( ^RP214-1-1 ) to ( ^RP214-1-9 ) are preferable. In the following chemical formula ( ^RP214 -1-9), np1 is an integer of 1 to 10.

In the general formula ( ^RP214-2 ), _RS is -SH, -SO _3H , or -S-, -C (= S)-, -S (= O)-, -S (=) in the structure. O) Represents a hydrocarbon group containing ₂ -or-S (= O) ₂ -O-.
R _S "hydrocarbons containing -S-, -C (= S)-, -S (= O)-, -S (= O) ₂ -or-S (= O) ₂ -O- in the structure As the hydrocarbon group in the "group", the "-O-, -C (= O)-, -C (= _O ) -O- or-in the structure of RO in the general formula ( ^RP15-1 )" is used. The same as the hydrocarbon group in "hydrocarbon group containing OH" can be mentioned.

As the group represented by the general formula ( ^RP214-2 ), the groups represented by the following chemical formulas ( ^RP214-2-1 ) to ( ^RP214-2-12 ) are preferable.

In the general formula ( ^RP214-3 ), RN represents a hydrocarbon group containing -NH ₂ or _-N =, -NH- or -C (= O) NH- in its structure.
The hydrocarbon group in the "hydrocarbon group containing -N =, -NH- or -C (= _O ) NH- in the structure" of ^{RN is the hydrocarbon group in the above general formula (RP214-1} ₎ . Examples thereof include the same hydrocarbon groups in "hydrocarbon groups containing -O-, -C (= O)-, -C (= O) -O- or -OH in the structure".

As the group represented by the general formula ( ^RP214-3 ), the groups represented by the following chemical formulas ( ^RP214-3-1 ) to ( ^RP214-3-12 ) are preferable.
In the formula ( ^RP214-3-2 ), ^RP2140 represents any organic group. The organic group of ^RP2140 is not particularly limited, and examples thereof include the same organic groups as those in the "organic group having a polar group" in the general formula (u2-1).

The R ^P214 in the general formula (u2-1-1) is the chemical formulas (R ^P214-1-1 ) to ( ^RP214-1-9 ) and the chemical formulas ( ^RP214-2-1 ) to ( ^RP214 ). -2-12) and at least one selected from the group consisting of the groups represented by any of the chemical formulas ( ^RP214-3-1 ) to ( ^RP214-3-12 ) are preferable.

A specific example of the structural unit (u21) is shown below.

A specific example of the structure represented by the general formula (1-1-2) will be described below.

(Constituent unit (u22))
The structural unit (u22) is not particularly limited as long as it is a structural unit containing a silicon atom other than the structural unit (u21), but the structural unit (221) derived from siloxane or the following general formula (u2-2-2). ) Is preferably the structural unit (u222), and more preferably the structural unit (221) derived from siloxane.

［式中、Ｒは、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｒ^Ｐ２２１は、２価の連結基である。Ｒ^Ｐ２２２は、ケイ素原子を有する有機基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. ^RP221 is a divalent linking group. ^RP222 is an organic group having a silicon atom. ]

(Constituent unit (221))
Examples of the constituent unit (221) include a constituent unit derived from dimethylsiloxane, a constituent unit derived from diethylsiloxane, a constituent unit derived from diphenylsiloxane, a constituent unit derived from methylphenylsiloxane, and the like. ..
Among them, the structural unit (u221) is preferably a structural unit derived from dimethylsiloxane.

(Constituent unit (222))
In the general formula (u2--2-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and the general formula (u2-1-1). It is the same as R in.
Among them, R is preferably a methyl group or a hydrogen atom.

In the general formula (u2--2-2), ^RP221 is a divalent linking group. Examples of the divalent linking group of ^RP221 include the same as the divalent linking group of ^RP213 in the general formula (u2-1-1). Among them, as the divalent linking group of ^RP221 , a divalent linking group containing a hetero atom or a divalent aromatic hydrocarbon group is preferable, and -O-, -C (= O) -O-,- C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H is an alkyl group or an acyl group) , Etc.), -S-, -S (= O) _2- , -S (= O) ₂ -O-, general formula-Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ^{21-C (= O) -O-, -C (= O) -O-Y 21-,-[Y 21 - C} (= O) -O] _{m "} -Y ^22- , -Y ²¹ -OC (= O) -Y ^{22- or -Y 21 -} S (= O) ₂ -O-Y ^22- [In the formula, Y ²¹ and Y ²² are Each is a divalent hydrocarbon group which may have a substituent independently, O is an oxygen atom, and m "is an integer of 0 to 3. ], A phenylene group, a naphthylene group, an anthrasenylene group or a phenanthrenylene group is more preferable, and an —C (= O) —O— or a phenylene group is further preferable.

In the general formula (u2--2-2), ^RP222 is an organic group having a silicon atom. The ^RP222 is not particularly limited, but at least one selected from the group consisting of organic groups represented by any of the following chemical formulas ( ^RP222 -1) to ( ^RP222 -3) is preferable.

［式中、Ｒ^０は、置換基を有していてもよい１価の炭化水素基を表す。複数のＲ^０はそれぞれ同じであってもよく異なっていてもよい。］

[In the formula, R ⁰ represents a monovalent hydrocarbon group which may have a substituent. The plurality of R ^0s may be the same or different. ]

In the general formula ( ^RP222-3 ), the monovalent hydrocarbon group which may have a substituent of ^R0 is the substitution exemplified in the description of ^RP211 in the general formula (u2-1). Examples thereof include monovalent hydrocarbon groups which may have a group. Of these, as ^R0 , an ethyl group or an isobutyl group is preferable.

In the present embodiment, the number average molecular weight (Mn) of the block copolymer (Mn) (polystyrene conversion standard by gel permeation chromatography) is preferably 5000 to 2000000, more preferably 5000 to 1000000. Is more preferable.
The dispersity (Mw / Mn) of the block copolymer is preferably 1.0 to 3.0, more preferably 1.0 to 1.5, and even more preferably 1.0 to 1.3. In addition, Mw indicates a mass average molecular weight.

In the present embodiment, the content ratio of the block (b22) is 1 to 50 mol% with respect to the total amount (100 mol%) of the first block, the block (b21), and the block (b22). It is preferably 1 to 45 mol%, more preferably 1 to 40 mol%, and even more preferably 1 to 40 mol%.
When the content ratio of the block (b22) is within the above range, the interface thickness between the first block and the block (b22) can be easily reduced, and the roughness of the pattern after dry etching can be reduced.
The content ratio of the first block is preferably 25 to 85 mol% with respect to the total amount (100 mol%) of the first block, the block (b21), and the block (b22). It is more preferably 30 to 80 mol%, still more preferably 40 to 70 mol%.
The content ratio of the block (b21) is preferably 5 to 45 mol% with respect to the total amount (100 mol%) of the first block, the block (b21) and the block (b22), and 10 to 10 to. 40 mol% is more preferred, and 15-35 mol% is even more preferred.

The block copolymer of the present embodiment can be suitably used as a resin composition for forming a phase-separated structure. When used as a resin composition for forming a phase separation, it is preferable to dissolve the block copolymer of the present embodiment in an organic solvent.

-Organic solvent The organic solvent may be any solvent as long as it can dissolve each component to be used to form a uniform solution, and is conventionally known as a solvent for a film composition containing a resin as a main component. One type or two or more types can be appropriately selected and used.
For example, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone, methyl-n- Ketones such as pentyl ketone, methyl isopentyl ketone, 2-heptanone (methyl amyl ketone); polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol A compound having an ester bond such as monoacetate or dipropylene glycol monoacetate, a monomethyl ether such as the polyhydric alcohol or the compound having the ester bond, a monoalkyl ether such as a monoethyl ether, a monopropyl ether, or a monobutyl ether, or a mono. Derivatives of polyhydric alcohols such as compounds having an ether bond such as phenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable]; cyclic ethers such as dioxane. And esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cre Examples thereof include aromatic organic solvents such as zirmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, simene and mesitylen.
These organic solvents may be used alone or as a mixed solvent of two or more kinds.
Of these, chloroform, 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and EL are preferable.
Further, a mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferably within the range. For example, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2. When PGME is blended as the polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3: 7 to 7 :. It is 3. When PGME and cyclohexanone are blended as the polar solvent, the mass ratio of PGMEA: (PGME + cyclohexanone) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3. : 7 to 7: 3.

Further, as the organic solvent in the resin composition for forming a phase separation structure, PGMEA, EL, or a mixed solvent of PGMEA and a polar solvent and a mixed solvent of γ-butyrolactone are also preferable. In this case, the mass ratio of the former and the latter is preferably 70:30 to 95: 5 as the mixing ratio.
The amount of the organic solvent used in the resin composition for forming a phase-separated structure is not particularly limited, and is a concentration that can be applied and is appropriately set according to the coating film thickness, but is generally a block. It is used so that the solid content concentration of the copolymer is in the range of 0.2 to 70% by mass, preferably 0.2 to 50% by mass.

The block copolymer of the present embodiment is suitable for self-assembled lithography because it can form a structure having a regular periodic structure by phase separation.
The block copolymer of the present embodiment includes the first block and the second block, and the second block includes the block (b21) and the block (b22).
Both the block (b21) and the block (b22) contain a silicon atom. Therefore, when a phase-separated structure is formed using the block copolymer of the present embodiment, the first block can be selectively removed by performing a dry etching process using oxygen plasma or the like.
The block (b22) is located between the first block and the block (b21). Therefore, when a phase-separated structure is formed using the block copolymer of the present embodiment and a pattern is formed by performing a dry etching process, the interface between the first block and the block (b22) is the edge portion of the pattern. Corresponds to. The block (b22) has a high repulsive interaction with the first block. Therefore, it is presumed that the interface thickness between the first block and the block (b22) can be reduced, and the roughness of the pattern after dry etching can be reduced.
Further, the surface free energy difference between the first block and the block (b21) is small. Therefore, it is presumed that when the block copolymer of the present embodiment is used to form a phase-separated structure, it is easy to form a vertical alignment pattern by thermal annealing.

≪Manufacturing method of block copolymer≫
In the method for producing a block copolymer of the present embodiment, a polymer having a repeating structure of a structural unit (u11) represented by the following general formula (u1-1) or a hydrogen atom bonded to a carbon atom at the α-position is used. A step (a) of preparing a first block composed of a polymer having a repeating structure of a structural unit (u12) derived from an acrylic acid ester which may be substituted with a substituent, and a step (a) prepared in the above step (a). A block copolymer precursor in which the first block and the block (b22) are bonded by addition polymerization of a siloxane or a monomer (m222) represented by the following general formula (m2-2-2) to the first block. A monomer (u21) that induces a structural unit (u21) represented by the following general formula (u2-1) in the step (b) for preparing the body and the block copolymer precursor prepared in the step (b). It has a step (c) of preparing a block copolymer in which the block (b22) is located between the first block and the block (b21) by addition polymerization of m21).

［式中、Ｒ^Ｐ１１１は、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ１１２は、置換基を有していてもよい芳香族環式基である。Ｒは、水素原子、炭素数１～５のアルキル基又は炭素数１～５のハロゲン化アルキル基である。Ｒ^Ｐ２２１は、２価の連結基である。Ｒ^Ｐ２２２は、ケイ素原子を有する有機基である。Ｒ^Ｐ２１１は、極性基を有する有機基、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ２１２は、極性基を有する有機基である。］

[In the formula, ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom. ^RP112 is an aromatic cyclic group which may have a substituent. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. ^RP221 is a divalent linking group. ^RP222 is an organic group having a silicon atom. ^RP211 is an organic group having a polar group, an alkyl group, an alkyl halide group or a hydrogen atom. ^RP212 is an organic group having a polar group. ]

In the general formula (u1-1), ^RP111 and ^RP112 are the same as described above.
In the general formula (m2-2-2), R, ^RP221 and ^RP222 are the same as R, ^RP221 and ^RP222 in the general formula (u2-2-2).
In the general formula (u2-1), ^RP211 and ^RP212 are the same as described above.

(Step (a))
In step (a), the first block is prepared. The method for preparing the first block is not particularly limited, and a known polymerization method can be used. For example, the monomer that induces the structural unit (u11) or the monomer that induces the structural unit (u12) can be polymerized in an organic solvent in the presence of a living anionic polymerization initiator such as sec-butyllithium (SecBuLi). can. The reaction temperature is not particularly limited, but a temperature at which the dispersity of the first block is narrowed is preferable.

(Step (b))
In the step (b), siloxane or the monomer (m222) is addition-polymerized to the first block prepared in the step (a), and the first block and the block (b22) are bonded to each other for block copolymerization. Prepare the precursor. The addition polymerization reaction in the step (b) can be carried out by a known method such as living anionic polymerization. The reaction temperature in the step (b) is not particularly limited, but it is preferably performed at 0 ° C. to 80 ° C. in consideration of the dispersion degree of the block copolymer precursor and the reaction temperature in the step (c), and 5 ° C. to 5 ° C. It is more preferably carried out at 60 ° C., and further preferably carried out at 10 ° C. to 40 ° C.

(Step (c))
In the step (c), the monomer (m21) is addition-polymerized to the block copolymer precursor prepared in the step (b), and a block (b22) is formed between the first block and the block (b21). ) Is located in the block copolymer.
In the step (c), the reaction temperature when the monomer (m21) is addition-polymerized to the block copolymer precursor is set to the siloxane or the monomer (m222) in the first block in the step (b). Is set to a temperature lower than the reaction temperature at the time of addition polymerization. This makes it possible to proceed with the addition polymerization reaction of the monomer (m21) in preference to the reaction of the siloxane remaining after the step (b) or the monomer (m22). As a result, it is possible to prepare a block copolymer in which the block (b22) is located between the first block and the block (b21).
The reaction temperature at the time of addition polymerization of the monomer (m21) to the block copolymer precursor is preferably a temperature at which the siloxane or the monomer (m22) does not react. Specifically, the reaction temperature at the time of addition polymerization of the monomer (m21) to the block copolymerization precursor is such that the siloxane or the monomer (m222) is added to the first block in the step (b). A temperature 20 ° C. or higher lower than the reaction temperature at the time of addition polymerization is preferable, a temperature 30 ° C. or higher lower is more preferable, and a temperature 40 ° C. or higher lower is further preferable.

The solvent used in the polymerization reaction of the steps (a), (b) and (c) is not particularly limited, but any compound used in each step may be soluble and may not react with the compound, for example. Examples thereof include tetrahydrofuran, N, N-dimethylformamide, dimethylacetamide, hexane, cyclohexane, toluene, N-methylpyrrolidone and the like.

In the present embodiment, instead of the step (c), the block copolymer precursor prepared in the step (b) is subjected to the structural unit (u21') represented by the following general formula (u2-1'). A step (c-) of adding and polymerizing a monomer (m21') that induces') to prepare a block copolymer in which the block (b22) is located between the first block and the block (b21'). By performing 1) and the step (c-2) of reacting the block copolymer prepared in the step (c-1) with a compound containing an organic group having a polar group, the first block and the block (c-2) are carried out. It is also possible to prepare a block copolymer precursor bonded to b22). In this case, in the step (c-1), the reaction temperature at the time of addition polymerization of the monomer (m21') to the block copolymerization precursor is set to the siloxane or the above-mentioned first block in the step (b). The temperature is set lower than the reaction temperature at the time of addition polymerization of the monomer (m222).

［式中、Ｒ^Ｐ２１１’は、反応性基を含む有機基、アルキル基、ハロゲン化アルキル基又は水素原子である。Ｒ^Ｐ２１２’は、反応性基を含む有機基である。］

[In the formula, ^RP211'is an organic group containing a reactive group, an alkyl group, an alkyl halide group or a hydrogen atom. ^RP212'is an organic group containing a reactive group. ]

(Step (c-1))
In the step (c-1), a monomer (u21') that induces a structural unit (u21') represented by the following general formula (u2-1') is derived from the block copolymer precursor prepared in the step (b). m21') is addition-polymerized to prepare a block copolymer in which the block (b22) is located between the first block and the block (b21').

In the general formula (u2-1'), ^RP211'is an organic group containing a reactive group, an alkyl group, an alkyl halide group or a hydrogen atom.
The "organic group containing a reactive group" also includes the reactive group itself.
A reactive group means a group that can react with other sites by a chemical reaction.
Reactive groups include vinyl group, allyl group, (meth) acryloyl group, styryl group, oxylanyl group, oxetanyl group, carboxy group, hydroxy group, thiacyclopropyl group, sulfanyl group, isocyanato group, amino group and ureido group. Can be mentioned. Among them, as the reactive group, a vinyl group and an allyl group are preferable, and a vinyl group is particularly preferable.
The organic group in ^RP211 ′ is not particularly limited, and examples thereof include the same as the monovalent hydrocarbon group which may have a substituent in ^RP211 ′ in the general formula (u2-1). ..
The alkyl group or halogenated alkyl group of ^RP211 ′ is the same as the alkyl group or halogenated alkyl group of ^RP211 in the general formula (u2-1).
Among them, ^RP211'is preferably an alkyl group, an alkyl halide group or a hydrogen atom, preferably an alkyl group having 1 to 5 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or a hydrogen atom, and preferably a methyl group or a hydrogen atom. Is the most preferable.

In the general formula ( ^u2-1 '), RP212'is an organic group containing a reactive group.
Examples of the organic group containing the reactive group of ^RP212 ′ include the same organic group containing the reactive group of ^RP211 ′.
Among them, as ^RP212 ', a vinyl group, an organic group having a vinyl group, and an allyl group are preferable, and a vinyl group is particularly preferable.

In the step (c-1), the reaction temperature at the time of addition-polymerizing the monomer (m21') to the block copolymer precursor is set to the siloxane or the monomer in the first block in the step (b). (M222) is set to a temperature lower than the reaction temperature at the time of addition polymerization. This makes it possible to proceed with the addition polymerization reaction of the monomer (m21') in preference to the reaction of the siloxane remaining after the step (b) or the monomer (m22). As a result, it is possible to prepare a block copolymer in which the block (b22) is located between the first block and the block (b21').

(Step (c-2))
In the step (c-2), the block copolymer prepared in the step (c-1) is reacted with a compound containing an organic group having a polar group. As a result, in the structural unit (u21') of the block ( ^b21 '), a polar group is introduced into the organic group containing the reactive group of ^{RP211'or RP212} ', and the first block and the block (b22) are bonded to each other. Block copolymerization precursor can be prepared.
The compound containing an organic group having a polar group is not particularly limited as long as it is a compound containing an organic group having a polar group of ^RP211 or ^RP212 in the general formula (u2-1). For example, when a compound having a thiol group and an organic group having a polar group is used, the polar group can be introduced into the organic group containing the reactive group of ^{RP211'or RP212} ' by the en-thiol reaction. ..

<< Method of forming a structure including a phase-separated structure >>
A method for forming a structure including a phase-separated structure using the block copolymer of the present embodiment will be described.
The method for producing a structure including a phase-separated structure includes a step (i) of forming a layer containing the block copolymer of the present embodiment on a substrate and a step of phase-separating the layer containing the block copolymer (i). ii) and.
In the method for producing a structure including the phase-separated structure of the present embodiment, a step of applying a base material to form a base material layer before the step (i) (hereinafter, “base material layer forming step”). It is preferable to have.
Hereinafter, a method for producing a structure including such a phase-separated structure will be specifically described with reference to FIG. However, the present invention is not limited to this.

FIG. 1 shows an example of an embodiment of a method for manufacturing a structure including a phase-separated structure.
First, a base material is applied onto the substrate 1 to form a base material layer 2 (FIG. 1 (I)).
Next, the block copolymer of the present embodiment described above is applied onto the base material layer 2 to form a layer (BCP layer) 3 containing the block copolymer (FIG. 1 (II); the above steps. (I)).
Next, heating is performed to perform annealing treatment, and the BCP layer 3 is phase-separated into phase 3a and phase 3b (FIG. 1 (III); step (ii)).
According to the manufacturing method of the present embodiment, that is, the manufacturing method including the step (i) and the step (ii), the structure 3'including the phase-separated structure is formed on the substrate 1 on which the base material layer 2 is formed. Manufactured.

[Step (i)]
In the step (i), the BCP layer 3 is formed on the substrate 1 by using the block copolymer.

The type of the substrate is not particularly limited as long as the block copolymer can be coated on the surface thereof.
Examples of the substrate include a substrate made of a metal such as silicon, copper, chromium, iron, and aluminum, a substrate made of an inorganic substance such as glass, titanium oxide, silica, and mica, an acrylic plate, polystyrene, cellulose, cellulose acetate, and phenol resin. Examples thereof include a substrate made of the above organic compound.
The size and shape of the substrate are not particularly limited. The substrate does not necessarily have to have a smooth surface, and substrates of various materials and shapes can be appropriately selected. For example, various shapes such as a substrate having a curved surface, a flat plate having an uneven surface, and a flaky shape can be used in various ways.
Inorganic and / or organic films may be provided on the surface of the substrate. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC).

The surface of the substrate 1 may be cleaned before forming the BCP layer 3 on the substrate 1. By cleaning the surface of the substrate, the resin composition for forming a phase-separated structure or the substrate can be better applied to the substrate 1.
As the cleaning treatment, conventionally known methods can be used, and examples thereof include oxygen plasma treatment, hydrogen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment. For example, the substrate is immersed in an acid solution such as a sulfuric acid / hydrogen peroxide aqueous solution, washed with water, and dried. After that, the BCP layer 3 or the base material layer 2 is formed on the surface of the substrate.

It is preferable to neutralize the substrate 1 before forming the BCP layer 3.
The neutralization treatment refers to a treatment of modifying the surface of a substrate so as to have an affinity with any of the polymers constituting the block copolymer. By performing the neutralization treatment, it is possible to prevent only the phase composed of a specific polymer from coming into contact with the surface of the substrate by phase separation. For example, before forming the BCP layer 3, it is preferable to form the substrate layer 2 on the surface of the substrate 1 according to the type of block copolymer used. Along with this, the phase separation of the BCP layer 3 facilitates the formation of a cylindrical or lamellar phase separation structure oriented in the direction perpendicular to the surface of the substrate 1.

Specifically, the base material layer 2 is formed on the surface of the substrate 1 by using a base material having an affinity with any polymer constituting the block copolymer.
As the base material, a conventionally known resin composition used for forming a thin film can be appropriately selected and used depending on the type of polymer constituting the block copolymer.
As such a base material, for example, a composition containing a resin having any of the constituent units of each polymer constituting the block copolymer, or a constituent unit having a high affinity with each polymer constituting the block copolymer is used. Examples thereof include a composition containing a resin having a resin.
For example, when a PS-PMMA block copolymer is used, as a base material, a resin composition containing both PS and PMMA, a site having a high affinity for an aromatic ring or the like, and a highly polar functional group or the like are compatible. It is preferable to use a compound or composition containing both a highly potent moiety and the like.
Examples of the resin composition containing both PS and PMMA include a random copolymer of PS and PMMA, an alternating polymer of PS and PMMA (one in which each monomer is alternately copolymerized), and the like.

Further, as a composition containing both a moiety having a high affinity for PS and a moiety having a high affinity for PMMA, for example, as a monomer, at least a monomer having an aromatic ring and a monomer having a highly polar substituent are used. Examples thereof include a resin composition obtained by polymerizing with. As the monomer having an aromatic ring, one hydrogen atom is removed from the ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, anthryl group, and a phenanthryl group. Examples thereof include a monomer having a group, or a monomer having a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is replaced with a hetero atom such as an oxygen atom, a sulfur atom and a nitrogen atom. Examples of the monomer having a highly polar substituent include a monomer having a carboxy group, a hydroxyl group, a cyano group, a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom, and the like.
Moreover, as a base material, for example, a photosensitive resin composition such as a thermopolymerizable resin composition, a positive type resist composition and a negative type resist composition can also be mentioned.

These base material layers can be formed by a conventional method.
The method of applying the base material onto the substrate 1 to form the base material layer 2 is not particularly limited, and can be formed by a conventionally known method.
For example, the base material layer 2 can be formed by applying the base material on the substrate 1 by a conventionally known method such as using a spin coat or a spinner to form a coating film and drying the coating film.
As a method for drying the coating film, it is sufficient that the solvent contained in the base material can be volatilized, and further, it is sufficient if it can be immobilized on the substrate, and examples thereof include a method of baking. At this time, the baking temperature is preferably 80 to 300 ° C, more preferably 90 to 270 ° C, and even more preferably 100 to 250 ° C. The baking time is preferably 30 to 500 seconds, more preferably 30 to 250 seconds.
The thickness of the base material layer 2 after the coating film is dried is preferably about 3 to 100 nm, more preferably about 5 to 50 nm.

Next, a layer (BCP layer) 3 containing a block copolymer in which a plurality of types of blocks are bonded is formed on the base material layer 2.
The method for forming the BCP layer 3 on the base material layer 2 is not particularly limited, and the resin composition is formed on the base material layer 2 by a conventionally known method such as using a spin coat or a spinner. Examples thereof include a method of applying to form a coating film and drying it.

As a method for drying the coating film of the resin composition, for example, 60 to 150 ° C. is preferable, 80 to 130 ° C. is more preferable, and the baking time is, for example, 10 to 3000 seconds, more preferably 20 to 120 seconds.

The thickness of the BCP layer 3 may be sufficient as long as it is sufficient for phase separation to occur, and the type of the substrate 1, the structural periodic size of the phase separation structure to be formed, the uniformity of the nanostructure, and the like are taken into consideration. Then, 10 to 100 nm is preferable, and 15 to 80 nm is more preferable.

[Step (ii)]
In the step (ii), the layer 3 containing the block copolymer formed on the substrate 1 is phase-separated.
By heating the substrate 1 after the step (i) and performing an annealing treatment, a phase-separated structure is formed in which at least a part of the surface of the substrate 1 is exposed by selective removal of the block copolymer. That is, a structure 3'containing a phase-separated structure in which the phase 3a and the phase 3b are phase-separated is manufactured on the substrate 1.
It is preferable that the temperature condition of the annealing treatment is equal to or higher than the glass transition temperature of the block copolymer used and lower than the thermal decomposition temperature. For example, when the block copolymer of the present embodiment is used, it is preferably 40 to 350 ° C, more preferably 50 to 300 ° C, and particularly preferably 70 to 120 ° C. The heating time is preferably 30 to 3600 seconds, more preferably 120 to 600 seconds.
Further, the annealing treatment is preferably performed in a gas having low reactivity such as nitrogen.

According to the method for producing a structure including a phase-separated structure according to the above-described embodiment, the phase separation performance of the block copolymer is enhanced, and a finer structure is better than the existing lithography technique. It can be formed by shape.
In addition, it is possible to manufacture a substrate having a nanostructure on the surface of the substrate whose position and orientation are designed more freely. For example, the formed structure tends to have a cylindrical or lamellar phase-separated structure oriented in a direction perpendicular to the substrate surface by appropriately controlling the affinity with the substrate.

[Arbitrary process]
The method for producing a structure including a phase-separated structure according to a second aspect of the present invention is not limited to the above-described embodiment, and includes steps (arbitrary steps) other than steps (i) to (ii). May be good.
As such an optional step, a step of selectively removing a phase consisting of at least one type of block among a plurality of types of blocks constituting the block copolymer among the BCP layer 3 (hereinafter, “step (iii)””. ), Guide pattern forming process and the like.

-About the step (iii) In the step (iii), the BCP layer 3 formed on the base material layer 2 is composed of at least one block among a plurality of types of blocks constituting the block copolymer. The phases (phase 3a, phase 3b) are selectively removed. As a result, a fine pattern (polymer nanostructure) is formed.

Examples of the method for selectively removing the phase composed of blocks include a method of performing oxygen plasma treatment on the BCP layer, a method of performing hydrogen plasma treatment, and the like.
In the following, among the blocks constituting the block copolymer, the block that is not selectively removed is referred to as a _{PA block, and the block that is selectively removed is referred to as a P B block} . For example, after phase-separating the layer containing the block copolymer of the present embodiment, the phase consisting of the second block is selectively removed by subjecting the layer to oxygen plasma treatment, hydrogen plasma treatment, or the like. .. In this case, the first block portion is the _{PA block and the second block portion is the P B block} .

FIG. 2 shows an example of an embodiment of the step (iii).
In the embodiment shown in FIG. 2, the phase 3a is selectively removed by performing oxygen plasma treatment on the structure 3'manufactured on the substrate 1 in the step (ii), and the structure 3b is composed of separated phases 3b. A pattern (polymer nanostructure) is formed. In this case, the phase 3b is a phase composed of a _{PA block, and the phase 3a is a phase composed of a P B block} .

The substrate 1 in which the pattern is formed by the phase separation of the BCP layer 3 as described above can be used as it is, but by further heating, the shape of the pattern (polymer nanostructure) on the substrate 1 can be used. Can also be changed.
The heating temperature condition is preferably equal to or higher than the glass transition temperature of the block copolymer used and lower than the thermal decomposition temperature. Further, the heating is preferably performed in a gas having low reactivity such as nitrogen.

-Regarding the guide pattern forming step In the method for manufacturing a structure including a phase-separated structure according to the second aspect of the present invention, even if there is a step of providing a guide pattern on the base material layer (guide pattern forming step). good. This makes it possible to control the arrangement structure of the phase-separated structure.
For example, even in a block copolymer in which a random fingerprint-like phase-separated structure is formed when a guide pattern is not provided, the groove structure of the resist film is provided on the surface of the base material layer along the groove. An oriented phase-separated structure is obtained. Based on such a principle, a guide pattern may be provided on the base material layer 2. Further, since the surface of the guide pattern has an affinity with any of the polymers constituting the block copolymer, it is easy to form a cylindrical or lamellar phase-separated structure oriented in the direction perpendicular to the substrate surface. Become.

The guide pattern can be formed using, for example, a resist composition.
As the resist composition forming the guide pattern, a resist composition generally used for forming the resist pattern or a modified product thereof having an affinity with any of the polymers constituting the block copolymer is appropriately selected. It can be selected and used. The resist composition includes a positive resist composition that forms a positive pattern in which the exposed portion of the resist film is dissolved and removed, and a negative resist composition that forms a negative pattern in which the unexposed portion of the resist film is dissolved and removed. Either may be used, but a negative resist composition is preferable. The negative resist composition contains, for example, an acid generator component and a base material component whose solubility in a developing solution containing an organic solvent is reduced by the action of the acid due to the action of the acid. However, a resist composition containing a resin component having a structural unit that is decomposed by the action of an acid and whose polarity is increased is preferable.
After the resin composition is poured onto the base material layer on which the guide pattern is formed, an annealing treatment is performed to cause phase separation. Therefore, it is preferable that the resist composition forming the guide pattern can form a resist film having excellent solvent resistance and heat resistance.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis Example 1: Synthesis of PS-b-PDMS-b-PMVS]
Under an Ar atmosphere, 10 ml of THF is charged into a reaction vessel and cooled to −78 ° C. After adding a predetermined amount of SecBuLi (mixed solution of hexane and cyclohexane) and 0.40 g of styrene, the mixture was stirred at −78 ° C. for 30 minutes. Then, after adding 0.40 g of hexamethylcyclotrisiloxane, the liquid temperature was changed to 20 ° C., and the mixture was stirred for 48 hours. Then, after changing the liquid temperature to −20 ° C., 0.40 g of trimethyltrivinylcyclotrisiloxane was added, and after further stirring for 48 hours, 0.20 g of trimethylsilyl chloride was added, and the reaction solution was added to 200 ml of methanol. The solid that was poured and precipitated was recovered by filtration. The recovered solid was dried to obtain 0.60 g of PS-b-PDMS-b-PMVS (hereinafter, "block copolymer (1')"). The Mn of the obtained block copolymer (1') was 15,000, the PDI was 1.10 (GPC equivalent), and the ratio of the repeating units of the obtained polymer was styrene: dimethylsiloxane: methylvinylsiloxane (n: l: l:). m) = 60:15:25 (mol ratio) ( ¹ H-NMR).

[Synthesis Example 2]
PS-b-PDMS-b-PMVS (hereinafter, "block copolymer (2')") was synthesized in the same manner as in Synthesis Example 1.
The Mn of the obtained block copolymer (2') was 18800, the PDI was 1.23 (GPC equivalent), and the ratio of the repeating units of the obtained polymer was styrene: dimethylsiloxane: methylvinylsiloxane (n: l: l:). m) = 52:18:30 (mol ratio) ( ¹ H-NMR).

[Synthesis Example 3]
PS-b-PDMS-b-PMVS (hereinafter, "block copolymer (3')") was synthesized in the same manner as in Synthesis Example 1.
The Mn of the obtained block copolymer (3') was 25100, the PDI was 1.22 (GPC equivalent), and the ratio of the repeating units of the obtained polymer was styrene: dimethylsiloxane: methylvinylsiloxane (n: l: l:). m) = 46: 35: 19 (mol ratio) ( ¹ H-NMR).

[Example 1: Synthesis of PS-b-PDMS-b-PMHxOHS]
0.10 g of block copolymer (1'), 0.007 g of azobisisobutyronitrile (AIBN), 0.54 g of 6-mercapto-1-hexanol and 0.8 ml of THF were charged in a reaction vessel and substituted with Ar. After that, freeze degassing was performed 3 times. After stirring at 65 ° C. for 4 hours, the mixture was rapidly cooled with an ice bath and liquid nitrogen, the reaction solution was poured into 100 ml of pure water, and the precipitated solid was recovered by filtration. The reprecipitation operation in pure water was repeated 3 times. The recovered solid was dried, and PS-b-PDMS-b-PMHxOHS (a block copolymer composed of a block of styrene, a block of dimethylsiloxane, and a block of siloxane derivative A, represented by the following structural formula. Hereinafter, "block". Copolymer (1) ") 0.11 g was obtained. The obtained block copolymer (1) had a Mn of 13400, a PDI of 1.12 (GPC equivalent), and a styrene: dimethylsiloxane: siloxane derivative A = 60: 15: 25 (mol ratio) ( ¹ H-NMR). there were.

[Example 2]
0.10 g of block copolymer (2'), 0.009 g of azobisisobutyronitrile (AIBN), 0.45 g of 3-mercapto-1-propanol and 0.8 ml of THF were charged in a reaction vessel and substituted with Ar. After that, freeze degassing was performed 3 times. After stirring at 65 ° C. for 4 hours, the mixture was rapidly cooled with an ice bath and liquid nitrogen, the reaction solution was poured into 100 ml of pure water, and the precipitated solid was recovered by filtration. The reprecipitation operation in pure water was repeated 3 times. A block copolymer composed of a styrene block, a dimethylsiloxane block, and a siloxane derivative B block, which is represented by the following structural formula after drying the recovered solid. Hereinafter, 1.1 g of "block copolymer (2)") was obtained. The obtained block copolymer (2) had a Mn of 16100, a PDI of 1.16 (GPC equivalent), and a styrene: dimethylsiloxane: siloxane derivative B = 52: 18:30 (mol ratio) ( ¹ H-NMR). there were.

[Example 3]
0.10 g of block copolymer (3'), 0.006 g of azobisisobutyronitrile (AIBN), 0.29 g of 3-mercapto-1-propanol and 0.8 ml of THF were charged in a reaction vessel and substituted with Ar. After that, freeze degassing was performed 3 times. After stirring at 65 ° C. for 4 hours, the mixture was rapidly cooled with an ice bath and liquid nitrogen, the reaction solution was poured into 100 ml of pure water, and the precipitated solid was recovered by filtration. The reprecipitation operation in pure water was repeated 3 times. A block copolymer composed of a styrene block, a dimethylsiloxane block, and a siloxane derivative B block, which is represented by the following structural formula after drying the recovered solid. Hereinafter, 1.1 g of "block copolymer (3)") was obtained. The obtained block copolymer (3) had a Mn of 21800, a PDI of 1.17 (GPC equivalent), and a styrene: dimethylsiloxane: siloxane derivative B = 46: 35: 19 (mol ratio) ( ¹ H-NMR). there were.

[Example 4: Formation of phase-separated structure]
A resin composition (Mw43400 and Mw / Mn1.77 consisting of methyl methacrylate / methacrylic acid = 95/5) adjusted to a concentration of 1.0% by mass using PGMEA as a base material on an 8-inch silicon wafer. The copolymer) was applied using a spinner, baked at 200 ° C. for 60 seconds, and dried to form a base material layer having a film thickness of 20 nm on the substrate.
Next, the portion of the base material layer other than the substrate adhesion portion is removed with a solvent (PGMEA), and the solution (solvent; PGMEA) of the block copolymer (1) is spin-coated on the base material layer (rotation speed 7500 rpm, 60 seconds). )did.
The coating film thickness of the layer containing the block copolymer (1) (hereinafter referred to as “resin composition layer for forming a phase-separated structure”) was 16 to 20 nm.
The substrate coated with the resin composition for forming a phase-separated structure was heated at 130 ° C. for 12 hours under a reduced pressure atmosphere and annealed to form a phase-separated structure.
After that, the block was selectively removed to form a line-and-space pattern.

<Evaluation of vertical orientation>
The surface of the pattern formed in Example 1 was observed with a scanning electron microscope SU8000 (manufactured by Hitachi High-Technologies Corporation), and the vertical orientation was evaluated according to the following evaluation criteria. The results are shown in Table 1.
◯: A phase separation structure perpendicular to the substrate was confirmed.
X: The phase separation structure perpendicular to the substrate could not be confirmed.

<Evaluation of roughness>
The solvent was removed from the block copolymer solution under reduced pressure, and the mixture was further heated at 110 ° C. for 24 hours under vacuum to obtain a film-like sample. After dyeing with ruthenium oxide, observation with TEM was performed, and roughness was evaluated according to the following criteria.
◯: No bridge connecting the lines was observed.
X: A bridge was observed.

[Examples 5 and 6]
A phase-separated structure was formed in the same manner as in Example 4 except that the block copolymer (2) or the block copolymer (3) was used instead of the block copolymer (1). After that, the block was selectively removed to form a line & space pattern. The formed patterns were evaluated for vertical orientation and roughness in the same manner as in Example 4. The results are shown in Table 1.

[Comparative Examples 1 to 3]
A phase-separated structure was formed in the same manner as in Example 4 except that the block copolymer (4), (1') or (5) shown below was used instead of the block copolymer (1). .. After that, the block was selectively removed to form a line & space pattern. The formed patterns were evaluated for vertical orientation and roughness in the same manner as in Example 4. The results are shown in Table 1.

表１に示す結果から、本発明を適用した実施例１～３のブロック共重合体垂直配向性が良好で、かつ、ラフネスも改善されていることが確認された。

From the results shown in Table 1, it was confirmed that the block copolymers of Examples 1 to 3 to which the present invention was applied had good vertical orientation and improved roughness.

Claims (7)

It is composed of a first block composed of a polymer having a repeating structure of a structural unit ( u11 ) represented by the following general formula (u1-1), and a polymer having a repeating structure of a structural unit (u2) containing a silicon atom. A block copolymer with a second block,
The second block is
A block (b21) made of a polymer having a repeating structure of a structural unit (u21) represented by the following general formula ( u2-1-1 ), and a block (b21).
A block (b22) composed of a polymer having a repeating structure of a structural unit ( u221 ) derived from dimethylsiloxane , and a block (b22).
Including
The block (b22) is a block copolymer located between the first block and the block (b21).

[In the formula, ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom. RP112 is ^an aromatic cyclic group which may have a substituent. ]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. RP213 is a ^divalent linking group. R ^P214 is a group represented by the following formula ( ^RP214 -1-9). ]

[In the formula, np1 is an integer from 1 to 10. * Indicates a bond that binds to the ^RP213 . ] The block copolymer according to claim 1 , wherein the number average molecular weight is 5000 to 2000000. The content ratio of the block (b22) is 1 to 50 mol% with respect to the total amount (100 mol%) of the first block, the block (b21), and the block (b22), claim 1 or 2. The block copolymer according to 2. The step (a) of preparing a first block composed of a polymer having a repeating structure of the structural unit (u11) represented by the following general formula (u1-1), and
The step (b) of preparing a block copolymer precursor in which the first block and the block (b22) are bonded by addition polymerization of dimethylsiloxane to the first block prepared in the step (a).
A monomer (m21) that induces a structural unit (u21) represented by the following general formula ( u2-1-1 ) is addition-polymerized to the block copolymer precursor prepared in the step (b). The step (c) of preparing a block copolymer in which the block (b22) is located between the first block and the block (b21), and
Have,
In the step (c), the reaction temperature when the monomer (m21) is addition-polymerized to the block copolymer precursor is set, and the reaction temperature when dimethylsiloxane is addition-polymerized in the first block in the step (b). The method for producing a block copolymer according to any one of claims 1 to 3, which is set to a temperature lower than the reaction temperature.

[In the formula, ^RP111 is an alkyl group, an alkyl halide group or a hydrogen atom. RP112 is ^an aromatic cyclic group which may have a substituent. ]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. RP213 is a ^divalent linking group. R ^P214 is a group represented by the following formula ( ^RP214 -1-9). ]

[In the formula, np1 is an integer from 1 to 10. * Indicates a bond that binds to the ^RP213 . ] The step (i) of forming a layer containing the block copolymer according to any one of claims 1 to 3 on the substrate, and
In the step (ii) of phase-separating the layer containing the block copolymer,
A method for producing a structure including a phase-separated structure. In the step (i), a base material is applied on a substrate to form a base material layer, and the block copolymer according to any one of claims 1 to 3 is contained on the base material layer. The method for producing a structure including the phase-separated structure according to claim 5 , which comprises an operation of forming a layer. The method for producing a structure including the phase-separated structure according to claim 5 or 6 , further comprising a step of forming a guide pattern on the substrate before the step (i).

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